Separation method for olefin alkylation



Sept. 13, 1955 w. F. ROLLMAN SEPARATION METHOD FOR OLEFIN ALKYLATION Filed Aug. 28, 1952 t, C? ESSE wm N z ...o mm 598m mm 596mm n 2 lv EJ xVlv 0 2 EI X 1 I Il www N E wzz .Nm 295959@ mmzoN w zoiw l. wm l N NN 9 N om Q9. 1 Immun m- Il N. ammi z mjo Mja/01er F. nPol'lvrzcm rave nf ar- )P'fv Mttornew United States Pat'ef SEPARATION METHOD FGR-A'OLEFIN f ALKYLATION i Walter F.- RollnanyCranford, `NJ'J.,z assignerI to -Esso Research and Engineering :Companygila corporation o-' Delaware Application August 28,'11952,',SerialNo.` 306,805

3 Claims. l" (Cl. 261K-683.4)

The present invention `relatesV to a method for-alkylatingim various organic materials with'oleiinic'hydrocarbons in the presence of a liquid catalystto produce alkylateduorganic' compounds'such as branched chain paraflic: hydrbcarbons; More particularly', the inventionA relatewsto van proved method for separating product andliquid acid'inl an alkylation process of thischaracterl Y Characteristically, vthe oleiinic4 materials contemplatedA by the present invention,'andcapable'l o'fentering intoan" alkylation reaction With compounds suchu as isoparatnici hydrocarbons, may also be polymerized' or degraded into sludge by contact Withthe catalyst materials employedfor alkylation.` In order to avoid the 'polymerization and' sludge forming reactions, or at least to Lreducethem to a 'e minimum when alkylation is desired, various process expedients have been employed. A conventional-fpm- 30 cedure to inhibit concurrent polymerization, aswell as to prevent other undesirable secondary or side reactions; has been to effect catalytic alkylation,reactionsunder conditions designed to avoid intimate contact of the olens with the catalyst material in thei comparative absence 'of iso-1 parains. To accomplish this, it has `be'en"customary' to' provide a substantial excess of isoparaflins in the reaction'V zon'e orto dilute the olefin material with a materialcon--f taining-.a substantially -Ygreater amount 'of soparafins prior 'to'introduction into the reaction zone.V Frexampla the olens -may bel dilutedormixed witha portieri-ofthe emulsion derived from -the -reaction- -zone"itselfandf recycled therefrom; or -the olefin i mat'erial' fmay fbe-introf duced in successive incrementsrina continuousseesfrof.- reactionzones or stages containing; previouslyemulsiedand contacted materials.

The above expediente, however, dosnotel-im-inatecornaf. pletelyI the polymerization of olens in an emulsion alkyla-ftion process. Conventionally, the emulsion Withdrawn from the reaction zone for product recovery is separated into its hydrocarbon and liquid acid components., `The hydrocarbon is sent to a product recovery system, and the acid is returned to the reactionzone Complete-separation isnot 'obtained since "substantial olensrenrain `dis`V solved in the' separatedacid;'ho'wever, substantially-'no parailinic hydrocarbons remain in the settledlacidfj The separated hydrocarbon phaseconsists 'chi'eily 'of nreacted isoparaflinsand -alkylat'e product; i Since-fthe@ emulsion i' separation ste'p requires an appreciable- `pe`riod= 'of ltii'r1"e,-it\ fr follows that the" olens dissolved inthe acid 'phasein the'72160 comparative` absenceof` isopar'a'fn'sgi Willf fundar-go the Y competing-polymerization'and sludgelformingreaotionsin 1 both 'the separation' zone and `the"lines lrecyclingt-lie' acid phase totherreactionzone.1v Consequently, polymerstcomff paratively floweini octan'e number` fin'dv their Iway into the@ alkya-te product -reducing the quality thereofr'i f The fsludfge L remainsinrth'e? acid, andfacid consumption fis 'increaseds f- Itis lanobjectlfof thefpresentfinvention to` provide'a systemffor carrying out' catalytic* reactions-offthe genert`1l-- character contemplated,` and especially to'provide ani improved` method '-forfseparatingf the :emulsion'l fromf'fthe-f alkylation process by means of which polymerization and other-'side reactions are reduced to a with a resultingimprove'ment 7in the yields and quality ofthe del sired' products# It is a further object of the invention to accomplish theseiimprovementsv by relatively simple `ex` pedient that entailsa minimum investment in new equip ment and equipment material balances and alk-ylation'units These and other'objects of the present changes and thatavoids changes in invention will become apparent from the following description taken inconnection "with the' sole ldrawing that illustrates a simplified flow plan of an alkylation system incorporating a preferred embodiment of ytheimproved` separation process.

In accordance with the present invention, the portion of the acid-hydrocarbon emulsion withdrawn from' the alk-ylation' reaction zone for product recovery is continuously charged to a separation zone. The resolution of the emulsion'fin the separation zone creates a top hydrocar-V bon layer including alkylate reaction products and unre# acted-'isoparains andf a bottom acid layer containing dis# solvedA olefns.r A portion of thewithdrawn hydrocarbon layer iscontinuously dispersed in the acid layer. The remaininglwithdrawn'hydrocarbon is set to product'recove'ry operations; Acid vis continuously Withdrawn from the acid layer-andlreturnedto the reactiorrzone.

The-continued introduction'ofa portion of the hydrocarbonl-'product-stream into the acid layer insures the presenceof 4excess isoparaiinsy in'the acidlayer at all times.'` This promotes alkylation of the dissolved olens and` minimizes' olelin"polymerization'and other degradation flreactin'sl Thelintroductionofhydrocarbon as a spray-into the settled acidv causes some turbulence in the" examplainfa typical alkylation freactionf,vessel t1 should be ofsuch-l Volume as to permit a residence time of the materalsfin"thl reactor'vessel of from about l minute to about 5 minutes.

Zone l11 is provided-With means for introducing liquid catalyst, olenand isoparainintoan emulsion pool including the'secomponents that is maintained Within the zone. In the apparatus as shown, olefin feed is introduced Vthrough'pipe or line 12-f`including control valve 13,"and a streamiof acid and isoparain are introduced byline 14. An emulsion phase Ais maintainedin zone 11 by Aany suitableagitating or contacting means such as-by recirculating -the emulsion at high turbulence, or by other meansfknown to the art.

A' portion of theemulsion, continuously withdrawn from the 'upper portion "of zone `11 through line l5, is passed throughbranchline 16 containing cooling means 17, 'for removal of lheat- 'of-reaction, `to"rnaintain the desired reaction temperature level,fand`is recycled back to tl'rezo'nel via line 18 containing' pump- 19 and line 14. Fresh *acidtcatalyst is added-to the system as needed through line 20 including 'controlvalve 21,: this acid conveniently being-addedtotherecycled'femulsion. Tsoparaflin' l'feedf may-` also lbe added to the yrecycled emulsion tion"zone'. The' Visopar'alin "includes `a fresh streamf Psientedeseprals, 1955- product recovery capacity in existing 3 product recovery system not shown, that passes through line 25.

A portion of the emulsion removed from reaction zone 11 by line 15 is withdrawn from the reaction system, for product recovery, by line 26 containing control valve 26 and pump 27, and is introduced into primary separation zone 28. Zone 28 may be any conventional type of separator or settling Vessel providing for the separation of an emulsion of immiscible materials into its respective lighter and heavier components. The emulsion layer 29 is intermediate the lighter hydrocarbon phase 30 including alkylate and unreacted isoparaiiins and the heavier acid phase 31 containing dissolved olefins. Acid phase is continuously withdrawn from zone 28 through line 32, containing control valve 32 and communicating with line 18, for recycling to reaction zone 11. Spent acid may be withdrawn from the system when necessary by line 33 including valvev 34.

Hydrocarbon phase is continuously withdrawn from zone 28 by means of line 35, and a portion thereof is charged through branch line 36 to a secondary separation zone 37. The remainder of the withdrawn hydrocarbon layer is passed through branch line 38 which contains control valve 39 and pump 40. Line 38 is fluidly connected to distribution means 41 positioned within separation zone 28 in the lower portion of acid phase 31. Distribution means 41 may be any suitable device for injecting the recycled hydrocarbon phase as a spray throughout substantially the entire acid phase. A cor-.- ventional pipe spider may be used, for example. Other arrangements may include injecting the hydrocarbon through porous thimbles and the like. The spray of injected hydrocarbons should be such that isoparatiin is maintained in intimate contact with the acid and dissolved olefin whereby alkylation of the oletins is promoted and oleiin degradation reactions are retarded. The hydrocarbons injected into the acid will, for the most part, pass upwardly through the acid and emulsion phases, recombine with the hydrocarbons in phase 30, and be withdrawn through line 35. Some of the injected hydrocarbons will be entrained in acid recycled to the reaction zone 11.

The hydrocarbon streams introduced through distribution means 41 may have sufficient velocity to create mild turbulence in emulsion phase 29 thereby promoting resolution of the emulsion. The injected hydrocarbon should not, however, disturb the resolution of the emulsion or agitate the contents of the settling zone sufficiently to cause remulsication of the separated components. By controlling the velocity and dispersion of the hydrocarbons, demulsitication may be aided whereby total retention time of the components in the separation zone is decreased and separation zone capacity is increased. This in some measure compensates for the additional settling zone volume required for hydrocarbons recycled to the acid phase.

The portion of the hydrocarbon phase charged to secondary settling zone 37 is subjected to a final settling step to remove any acid entrained therein. Settled acid may be withdrawn through line 44 containing valve 46 and recycled to the reaction zone 11 through lines 1S and 14. Hydrocarbon is withdrawn through line 4S and passed to a conventional product recovery system not shown. This recovery system may include a neutralization zone for neutralizing and removing any acidic constituents from the hydrocarbon, and a fractionation zone for separating the hydrocarbon into alkylate product and a stream concentrated in isoparafin. The recovered isoparaffin stream may be recycled to the reaction system through line as heretofore described.

If desired, zone 37 may be provided with means for recycling some separated hydrocarbon back to the acid phase as described in connection with the system for zone 28. This operation would be desirable only when the amount of acid carried into zone 37 is sufficient to create olefin degradation difficulties. Obviously, separation zone 28 may consist of one large vessel or of a plurality of vessels operating in series or in parallel.

The system as illustrated is suitable for employment under any circumstances in which two or more substantially immiscible materials of different specific gravitics are to be contacted, and is particularly useful under circumstances in which such contact is made for the purpose of initiating a chemical reaction involving the materials, in which the reactants and the reaction products may be separated from the catalyst material employed by gravity; and in which a more reactive component such as oletins dissolves to some extent in the separated catalyst material. More speciiically, the system is adapted for employment in the alkylation of isoparaiiins with an olefin, in the presence of a liquid active acid catalyst material such as concentrated sulfuric acid. For example, the system is suitable for the alkylation of butylenes with isobutane in the presence of sulfuric acid having a strength of from about 90 to about 98%, in which the alkylation reaction is carried out at a temperature of from about 30 to about 60 F. In such a reaction, it is desirable that the isobutane be present in the reactant materials in an amount considerably in excess of the butylene in order to insure substantially complete utilization of the latter material. It is also desirable that the operation provide against uncontrolled polymerization of the butylene component.

In a typical operation, isoparatiins and olens may be introduced into the system in such proportions as to result in a total feed in which the several components are present substantially as follows:

Component: Per cent total feed C3 3 Butylene 15 Isobutane 70 Normal butane 12 Normally, the olefin material initially fed into the system through line 12 may be supplied by a composition substantially as follows:

Component: Per cent total feed C3 l Butylene 40 Isobutane 47 Normal butane 12 In order to achieve the desired proportions of butylenes to isobutane in the reaction mixture, additional butane willbe made available from some other source. The material passing through line 23 may have a composition substantially as follows:

Component: Per cent total feed C3 3 Isobutane Normal butane 12 A suitable feed material also may be obtained by recycling unreacted isobutane through line 25, this recycled stream being recovered from the product stream as heretofore described.

In an operation in which about 5000 barrels per day (B/D) of alkylate product are produced, about 30,000 B/D of sulfuric acid is handled by reaction zone 11. The total isobutane handled is about 70,000 B/D, and about 3000 B/ D of fresh isobutane will be needed. About 7000 B/D of butylene feed will be used. About 20,000 B/D of emulsion including about 4000 B/D of acid will be withdrawn through line 26 from the reaction system and passed to settling zone 28. The acid settling in zone 28 contains about 400 B/D of dissolved oletins. The separated hydrocarbon withdrawn through line 35 represents about 16,500 B/D, of which approximately 50% is isobutane. Approximately 2000 B/D of the separated hydrocarbon is recycled through distribution means 41 into the settled acid layer, thus maintaining a molar excess of isoparatln over olefin in the settled acid. Whereas, under conventional conditions, the alkylate product will contain several hundred B/D of low octane polymer and the like, the above modification effects a substantial reduction in the amount of low octane materials formed. Thus, alkylate octane number may be increased by several tenths of a point and acid consumption decreased by a substantial amount. Furthermore, this mode of operation does not change the inventory of hydrocarbons in the system. If extraneous isobutane were charged to the acid layer in zone 28, product fractionation capacity would have to be increased by as much as 1000 B/D to achieve the same results. The mode of the present invention thus provides improved product quality, increased life of catalyst and economies in processing to achieve the desired results.

While the above specific example illustrates a typical alkylation operation, it is not desired to be bound by the speciic reaction conditions and proportions of reactants set forth. As will be obvious to one skilled in the art, various ratios of catalyst to reactants and various ratios of reactant components may be used to obtain suitable products.

The amount of separated hydrocarbon to be recycled to the settled acid phase may be varied over a rather wide range depending on such factors as the olen content of the settled acid, the degree of intimacy of contact obtained in the acid phase and the like. Generally, it is desired to recycle sutiicient hydrocarbon to supply at least a molar excess of isoparatiin over the olefin dissolved in the acid when good contact between dispersed hydrocarbon and acid is obtained. The ratio of dispersed isoparaflin to dissolved olefin may be as high as 5:1 or higher if necessary. The ratios will be limited to some extent by the capacity of the settling zone, and it is not desired to employ a ratio suiciently high to increase unduly settling zone capacity. With proper recycle hydrocarbon contacting and dispersing means, existing settling zones may be adapted to the present process, since'the amount of recycled hydrocarbon is relatively low in comparison to total throughput through the settling zone.

Although the example specifically discloses alkylation of isobutane with butylene in the presence of sulfuric acid as catalyst, the present invention contemplates simi lar operations employing other suitable paraflinic and olenic materials, including isopentane, propylene and amylenes. Other suitable liquid catalysts include hydrouoric acid, mixtures of sulfuric and phosphoric acids, as well as certain complexes of aluminum chloride and boron fluoride.

What is claimed is:

l. In the process of reacting isoparainc hydrocarbons with olenic hydrocarbons in the presence of an acid catalyst to form branched chain saturated hydrocarbons, which comprises contacting an emulsied body of said reactant materials and catalyst in a conned reaction zone under reaction conditions, continuously withdrawing a portion of the emulsied body from said zone, charging said withdrawn emulsion to a settling zone wherein it is separated into a catalyst layer containing dissolved olens and a hydrocarbon layer including reaction product and unreacted isoparains, returning said separated catalyst layer to said reaction zone and withdrawing said hydrocarbon layer, the improvement which comprises continuously dispersing a portion of said withdrawn hydrocarbon layer through said catalyst layer within said settling zone whereby undesirable reactions of said dissolved olens are minimized.

2. A process as in claim 1 wherein the amount of said hydrocarbon layer dispersed in said catalyst layer is sucient to provide at least a molar excess of said unreacted isoparans over said dissolved oleiins.

3 A process as in claim 2 wherein is sulfuric acid.

said acid catalyst References Cited in the le of this patent UNITED STATES PATENTS 2,313,660 Montgomery Mar. 9, 1943 2,389,604 Dowding Nov. 27, 1945 2,428,506 Van Der Valk Oct. 7, 1947 2,454,869 Goldsby et al. Nov. 30, 1948 

1. IN THE PROCESS OF REACTING ISOPARAFFINIC HYDROCARBONS WITH OLEFINIC HYDROCARBONS IN THE PRESENCE OF AN ACID CATALYST TO FORM BRANCHED CHAIN SATURATED HYDROCARBONS, WHICH COMPRISES CONTACTING AN EMULSIFIED BODY OF SAID REACTANT MATERIALS AND CATALYST IN A CONFINED REACTION ZONE UNDER REACTION CONDITIONS, CONTINUOUSLY WITHDRAWING A PORTION OF THE EMULSIFIED BODY FROM SAID ZONE, CHARGING SAID WITHDRAWN EMULSION TO A SETTLING ZONE WHEREIN IT IS SEPARATED INTO A CATALYST LAYER CONTAINING DISSOLVED OLEFINS AND A HYDROCARBON LAYER INCLUDING REACTION PRODUCT AND UNREACTED ISOPARAFFINS, RETURNING SAID SEPARATED CATALYST LAYER TO SAID REACTION ZONE AND WITHDRAWING SAID HYDROCARBON LAYER, THE IMPROVEMENT WHICH COMPRISES CONTINUOUSLY DISPERSING A PORTION OF SAID WITHDRAWN HYDROCARBON LAYER THROUGH SAID CATALYST LAYER WITHIN SAID SETTLING ZONE WHEREBY UNDESIRABLE REACTIONS OF SAID DISSOLVED OLEFINS ARE MINIMIZED. 